EP1623634A1 - Procédé de production de tabac régénéré - Google Patents
Procédé de production de tabac régénéré Download PDFInfo
- Publication number
- EP1623634A1 EP1623634A1 EP04729526A EP04729526A EP1623634A1 EP 1623634 A1 EP1623634 A1 EP 1623634A1 EP 04729526 A EP04729526 A EP 04729526A EP 04729526 A EP04729526 A EP 04729526A EP 1623634 A1 EP1623634 A1 EP 1623634A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fraction
- membrane
- tobacco
- extracted solution
- regenerated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 235000002637 Nicotiana tabacum Nutrition 0.000 title claims abstract description 224
- 241000208125 Nicotiana Species 0.000 title claims abstract description 222
- 239000000463 material Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims description 36
- 238000000605 extraction Methods 0.000 claims abstract description 37
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- 238000001223 reverse osmosis Methods 0.000 claims abstract description 24
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- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims description 140
- 239000012466 permeate Substances 0.000 claims description 79
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- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 claims description 67
- 229960002715 nicotine Drugs 0.000 claims description 67
- -1 nitrate ions Chemical class 0.000 claims description 27
- 229910002651 NO3 Inorganic materials 0.000 claims description 22
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 claims description 7
- 210000003918 fraction a Anatomy 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
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- 235000019504 cigarettes Nutrition 0.000 description 30
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- 238000005194 fractionation Methods 0.000 description 11
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- 238000010438 heat treatment Methods 0.000 description 5
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- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 210000002196 fr. b Anatomy 0.000 description 3
- 210000000540 fraction c Anatomy 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 244000061176 Nicotiana tabacum Species 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- 235000013355 food flavoring agent Nutrition 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZJOFAFWTOKDIFH-JTQLQIEISA-N 3-[(2s)-1-nitroso-3,6-dihydro-2h-pyridin-2-yl]pyridine Chemical compound O=NN1CC=CC[C@H]1C1=CC=CN=C1 ZJOFAFWTOKDIFH-JTQLQIEISA-N 0.000 description 1
- BXYPVKMROLGXJI-JTQLQIEISA-N 3-[(2s)-1-nitrosopiperidin-2-yl]pyridine Chemical compound O=NN1CCCC[C@H]1C1=CC=CN=C1 BXYPVKMROLGXJI-JTQLQIEISA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 101150096839 Fcmr gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229930013930 alkaloid Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000005454 flavour additive Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- XKABJYQDMJTNGQ-VIFPVBQESA-N n-nitrosonornicotine Chemical compound O=NN1CCC[C@H]1C1=CC=CN=C1 XKABJYQDMJTNGQ-VIFPVBQESA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/12—Chemical features of tobacco products or tobacco substitutes of reconstituted tobacco
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/24—Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
Definitions
- the present invention relates to a method of manufacturing a regenerated tobacco material.
- U.S. Patent No. 4,253,929 and U.S. Patent No. 4,364,401 disclose a method in which tobacco materials are extracted with an aqueous extracting solvent, followed by subjecting the extracted aqueous solution to an electrodialysis to separate and remove the nitrate ions.
- Various tobacco articles can be manufactured by adding the extracted solution, having the nitrate ions removed therefrom, to the extraction residue forming fibrous tobacco materials.
- U.S. Patent Publication US 2002/0134394 A1 (corresponding to International Publication WO 02/28209 discloses a method in which an extracted solution obtained by extracting tobacco materials with an extracting solvent is treated with a sorption agent capable of adsorbing/absorbing nitrosamines, such as activated carbon, to remove nitrosamines from the extracted solution.
- a sorption agent capable of adsorbing/absorbing nitrosamines, such as activated carbon
- the object that is to be removed is limited to ions and, thus, the method cannot be used widely.
- the extracted solution tends to be denatured by the voltage application during the electrodialysis.
- the extracted solution also tends to be denatured by heating that is applied for improving the separation efficiency.
- an object of the present invention is to provide a method of manufacturing a regenerated tobacco material, in which a fraction rich in a desired component and poor in an undesired component and another fraction poor in the desired component and rich in the undesired component are obtained from an extracted solution extracted from natural tobacco materials, and one or both of these fractions are used to manufacture the regenerated tobacco materials.
- a method of manufacturing a regenerated tobacco material comprising the steps of (a) extracting a natural tobacco material with an extracting solvent to obtain an extracted solution containing components of the natural tobacco material and an extraction residue, the natural tobacco materials containing both desired components and undesired components, (b) fractionating the extracted solution by means of ultrafiltration, reverse osmosis filtration, or reversed-phase partition chromatography to obtain a first fraction enriched in the desired components and depleted in the undesired components and a second fraction enriched in the undesired components and depleted in the desired components, (c) preparing a regenerated tobacco web by using the extraction residue, and (d) adding the first fraction to the regenerated tobacco web optionally together with the second fraction decreased in amount.
- the present invention relates to a method of manufacturing a regenerated tobacco material by using an extracted solution and an extraction residue obtained by subjecting a natural tobacco material to extraction.
- a regenerated tobacco web is prepared by using the extraction residue.
- the extracted solution is subjected to a fractionating operation by means of ultrafiltration, reverse osmosis filtration, or reversed-phase partition chromatography.
- the extracted solution obtained from the natural tobacco material contains those which are desirable to be decreased in amount or to be removed (undesired components), on one hand, and also include those which are desirable not to be removed or to be increased in amount (desired components), in view of the tobacco flavor or some other reasons.
- the fractionating operation according to the present invention there are obtained a first fraction, which is enriched in the desired components and depleted in the undesired components, and a second fraction, which is enriched in the undesired components and depleted in the desired components.
- a desired regenerated tobacco material is manufactured by adding the first fraction to the regenerated tobacco web optionally together with the second fraction decreased in amount.
- FIG. 1 is a flowchart for explaining a method of manufacturing a regenerated tobacco material according to one embodiment of the present invention.
- the fractionating operation to the extracted solution is carried out by means of the ultrafiltration or reverse osmosis filtration.
- a natural tobacco material 11 is mixed with an extracting solvent 12, and the mixture is stirred so as to subject the natural tobacco material 11 to an extracting treatment S1.
- the natural tobacco material 11 use may be made of the leaf, the shredded leaves, central vein, the stalk, and the root of the tobacco plant as well as a mixture thereof.
- Water or an organic solvent for example, may be used as the extracting solvent.
- the extracting solvent such as water may be alkaline or acidic.
- the extracting solvent a mixture of water and an organic solvent that is miscible with water may also be used.
- the organic solvent include, for example, alcohols such as ethanol, ethers such as diethyl ether, and hydrocarbon solvents such as cyclohexane.
- An inorganic salt such as sodium hydroxide may be dissolved in the extracting solvent.
- the extracting treatment is carried out at a temperature of 0 to 100°C for 5 minutes to 6 hours.
- the extracted mixture obtained is subjected to a separating treatment S2 by, for example, filtration to separate the extracted mixture into an extracted solution 13 and an extraction residue 14.
- the natural tobacco material contains salts of metals such as potassium salt, nitrates, nicotine, sugars, amino acids, glycoside, amino-sugar compounds, proteins, hydrocarbons (saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons), alcohols, ethers, aldehydes, ketones, esters, lactones, quinones, acids (including acid anhydrides), phenols, amines, pyrroles, pyridines, pyrazines, alkaloids, polycyclic nitrogen-containing compounds, nitroso compounds such as nitrosamines (including tobacco-specific nitrosamines (TSNAs), amides, lipids, halides, sulfur-containing compounds, and inorganic elements.
- metals such as potassium salt, nitrates, nicotine, sugars, amino acids, glycoside, amino-sugar compounds, proteins, hydrocarbons (saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons), alcohols, ethers, aldeh
- the extracted solution 13 obtained by the extracting treatment noted above can contain substantially all of the components mentioned above, though depending on the extracting solvent used.
- which components are the desired components and which components are the undesired components vary depending on, for example, the desired taste or flavor of the regenerated tobacco material that is to be manufactured.
- at least nicotine is the desired component
- nitrates and amines including nitrosamines such as TSNAs are the undesired components.
- the extraction residue 14 is a component insoluble in the extracting solvent and consists essentially of fibers.
- a regenerated tobacco web is manufactured by an ordinary method by using the extraction residue 14.
- the extraction residue may constitute the entire regenerated tobacco web or a part of the regenerated tobacco web.
- a regenerated tobacco web 15 can be obtained by subjecting pulp material containing the extraction residue 14 to an ordinary paper-making process S3.
- the membrane separating treatment S4 is performed by ultrafiltration or reverse osmosis filtration.
- the membranes used for the membrane separating treatment i.e., the ultrafiltration membrane and the reverse osmosis filtration membrane
- the membranes used for the membrane separating treatment are porous membranes provided with pores having a prescribed size or less, and separate and fractionate solutes based mainly on the difference in size between the pore of the membrane and the solute molecules.
- the molecular weight of the smallest solute that is incapable of passing through the membrane is called the cut-off molecular weight of the membrane.
- the cut-off molecular weight of the ultrafiltration membrane is 1,000 to 1,000,000, and the cut-off molecular weight of the reverse osmosis filtration membrane is 100 to 1,000.
- these membranes are commercially available.
- the ultrafiltration membrane use may be made of Biomax 5 (a cut-off molecular weight of 5,000) and PCXK cellulose (a cut-off molecular weight of 1,000,000), available from Milipore Inc.
- the reverse osmosis filtration membrane use may be made of Nanomax 95 (a cut-off molecular weight of about 100) and Nanomax 50 (a cut-off molecular weight of about 400), available from Milipore Inc.
- the membrane separation by the ultrafiltration and the reverse osmosis filtration can be performed by the procedures known pre se in the art.
- the extracted solution 13 may be at a low temperature of 0°C to 30°C, with the result that the components contained in the extracted solution are unlikely to be denatured.
- the reverse osmosis filtration membrane (reverse osmosis membrane) is capable of efficiently separating hydrated ions such as nitrate ions.
- the membrane non-permeate fraction 16 is enriched in those natural tobacco components which have a molecular weight larger than the cut-off molecular weight of the membrane used and depleted in those natural tobacco components which have a molecular weight smaller than the cut-off molecular weight of the membrane used, compared with the membrane permeate fraction 17.
- the membrane permeate fraction 17 is enriched in those natural tobacco components which have a molecular weight smaller than the cut-off molecular weight of the membrane used and depleted in those natural tobacco components which have a molecular weight larger than the cut-off molecular weight of the membrane used, compared with the membrane non-permeate fraction 16. Whether the fraction 16 or 17 is enriched or depleted in the natural tobacco components is determined on the basis of the relative concentration/amount of the natural tobacco components.
- the membrane non-permeate fraction 16 and/or the membrane permeate fraction 17 may be subjected to an additional treatment (not shown).
- the additional treatment includes, for example, at least one additional membrane separating treatment similar to that described above, the component separation by the chromatography, the concentrating treatment, and the component removal by using an adsorbent.
- the membrane non-permeate fraction and/or the membrane permeate fraction can be discarded, if these fractions are undesirable, and can be used as they are, or mixed (S5) with the other fraction to adjust the tobacco taste or flavor, if these fractions are desirable.
- S5 mixed with the other fraction to adjust the tobacco taste or flavor
- a regenerated tobacco material 18 can be obtained by adding the tobacco flavoring agent thus prepared to the regenerated tobacco web (S6).
- the regenerated tobacco material 18 thus obtained produces a taste or flavor differing from that of the natural tobacco material in spite of the fact that the regenerated tobacco material 18 contains components derived from the natural tobacco material.
- the membrane separating treatment is carried out a plurality of times by using ultrafiltration membranes or reverse osmosis filtration membranes differing from each other in the cut-off molecular weight, it is possible to add a single or a plurality of the resultant membrane non-permeate fractions and the membrane permeate fractions to the regenerated tobacco web.
- the amount of at least one of the membrane non-permeate fraction and the membrane permeate fraction is decreased in adding these fractions to the regenerated tobacco web.
- a first example covers the case where the amount of the nitrate contained in the natural tobacco material is decreased.
- a water-extracted solution obtained by extracting the natural tobacco material with water is subjected to a membrane extracting treatment using a reverse osmosis filtration membrane having a cut-off molecular weight of about 400.
- a membrane non-permeate fraction enriched in those tobacco components which have a molecular weight exceeding 400 in other words, depleted in those components which have a molecular weight not larger than 400 including inorganic ions such as nitrate ions and potassium ions).
- a membrane permeate fraction depleted in those tobacco components which have a molecular weight exceeding 400 in other words, enriched in those components which have a molecular weight not larger than 400 including inorganic ions such as nitrate ions and potassium ions. It is possible to add singly the membrane non-permeate fraction depleted in the nitrate ions to the regenerated tobacco material prepared by using the extraction residue or to mix the membrane non-permeate fraction with a small amount of the membrane permeate fraction for addition to the regenerated tobacco material prepared by using the extraction residue.
- the cigarette manufactured by using the particular regenerated tobacco material permits markedly decreasing the amount of NOx contained in the mainstream smoke and also permits lowering the burn rate, compared with the cigarette manufactured by using the natural tobacco material.
- a second example is directed to a membrane separation of the liquid extract of natural tobacco material extracted with water.
- used is a reverse osmosis filtration membrane having a cut-off molecular weight of about 100.
- the cigarette manufactured by using the regenerated tobacco material prepared by adding the membrane non-permeate fraction to the regenerated tobacco web retains tobacco-likeness or the tobacco-likeness is relatively increased.
- the amount of nitrate ions is decreased, the amount of NOx contained in the mainstream smoke is also decreased.
- the membrane non-permeate fraction which is enriched in nicotine
- nitrosamines such as TSNAs
- the additional treatment noted above includes the separation by the chromatography and the removal of the nitrosamine by the sorption treatment using a nitrosamine sorption agent.
- the removal of the nitrosamine can also be applied to the membrane permeate fraction in the first example described above.
- a third example is directed to the fractionation of the extracted solution by using two kinds of membranes.
- the extracted solution obtained by extracting the natural tobacco components with water is subjected to the membrane separating treatment using a reverse osmosis filtration membrane having a cut-off molecular weight of 100 so as to obtain a membrane non-permeate fraction (fraction A) having the amount of nitrate ions decreased as in the second example described above and a membrane permeate fraction enriched in the nitrate ions.
- the fraction A is subjected to the membrane separating treatment using an ultrafiltration membrane having a cut-off molecular weight of about 5,000 so as to obtain a membrane non-permeate fraction (fraction B) and a membrane permeate fraction (fraction C).
- the fraction B is enriched in proteins
- the fraction C is enriched in sugars such as sucrose.
- the fraction C is added, as required, to a small amount of the fraction A and/or the fraction B, and the resultant fraction mixture is added to the regenerated tobacco web so as to prepare the regenerated tobacco material. If a cigarette is manufactured by using the regenerated tobacco material thus prepared, it is possible to obtain a cigarette having the sweetness emphasized relatively.
- FIG. 2 is a flowchart for explaining a method of manufacturing a regenerated tobacco material according to another embodiment of the present invention.
- the reference numerals used commonly in FIGS. 1 and 2 denote the same factor and the treatment required for the manufacture of the regenerated tobacco material.
- the fractionating treatment of the extracted solution is carried out by reversed-phase partition chromatography. Nicotine and TSNAs can be effectively separated by the fractionating treatment of the extracted solution carried out by the reversed-phase partition chromatography.
- the present inventors have paid attention to chromatography as a simple procedure for separating nicotine from TSNAs in the extracted solution obtained by extracting the natural tobacco material with an aqueous extracting solvent.
- the chromatography includes a size chromatography in which an eluting solution is allowed to flow into a column loaded with a loading material having pores of a prescribed size so as to separate desired components by utilizing the difference in the eluting rate that is determined by the size and shape of the molecules.
- nicotine and TSNAs are close to each other in properties, it was difficult to separate these components by the size chromatography.
- the salt concentration of the eluting solution requires pH control for separating nicotine and TSNAs adsorbed on the loading material from each other. In the case of simply using an aqueous eluting solution, it was impossible to separate nicotine and TSNA from each other.
- the present inventors have conducted a further research to find that the reversed-phase partition chromatography makes it possible to separate effectively nicotine and TSNA from each other even in the case of using an aqueous eluting solution.
- the extracted solution 13 and the extraction residue 14 are obtained by the extracting treatment S1 using the extracting solvent 12 as described previously in conjunction with FIG. 1.
- the regenerated tobacco web 15 can be prepared by the paper-making process S3 using the extraction residue 14 as described previously in conjunction with FIG. 1.
- the extracted solution 13 obtained by the separating treatment S2 is subjected to a separating treatment S21 that is carried out by the reversed-phase partition chromatography.
- the separating treatment S21 can be carried out by using a stationary phase using a (meth)acrylic series rein, a vinyl series resin or a silica series resin as a base material. It is desirable for the base material to have a hydrophobic group.
- the hydrophobic group is desirably a hydrocarbon group having at most six carbon atoms. A hydrocarbon group having six or less carbon atoms is certainly hydrophobic.
- the hydrocarbon groups having at most six carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group.
- the hydrophobic group may be the one that is introduced to modify the base material or the one that is originally included in the base material such as the methyl group of the methacrylic acid portion constituting a polymethacrylic acid-based resin.
- the stationary phase material having such a hydrophobic group which is used in the reversed-phase partition chromatography, is commercially available in the form of a granular material.
- the tobacco extracted solution is poured into a column loaded with the stationary phase described above, followed by fractionating the tobacco extracted solution by using an aqueous eluent.
- the aqueous eluent can be provided by water or a mixture of water and an organic solvent miscible with water (e.g., ethanol).
- the reversed-phase partition chromatography can be carried out at a temperature lower than the boiling point of the solvent (e.g., 10 to 90°C).
- a fraction 21 (nicotine-containing, TSNA-removed fraction) containing a significant amount of nicotine (e.g., at least 30% of the initial nicotine content), and having TSNAs substantially removed therefrom is recovered from the fractions flowing out of the column by the reversed-phase partition chromatography, and the a fraction 22 (TSNA fraction) containing a significant amount of TSNAs is discarded.
- a fraction 22 (TSNA fraction) containing a significant amount of TSNAs is discarded.
- a fraction having a TSNA reduction rate of at least about 90% and having a nicotine reduction rate lower than 60% compared with the extracted solution before the fractionation.
- a stationary phase material having a hydrophobic group consisting of a hydrocarbon group having at most six carbon atoms it is possible to obtain a fraction having a TSNA reduction rate not lower than about 90% and having a nicotine reduction rate lower than 35%.
- a regenerated tobacco material 23 can be obtained, when the nicotine-containing TSNA-removed fraction 21, which is concentrated or not concentrated, is added (S22) partly or entirely to the regenerated tobacco web 15.
- the regenerated tobacco material 23 thus obtained contains nicotine, but is substantially free from TSNAs.
- the membrane permeate fraction or the membrane non-permeate fraction obtained in the first embodiment is subjected to the fractionating treatment by the reversed-phase partition chromatography employed in the second embodiment.
- the membrane permeate fraction obtained in the first embodiment and enriched in both nicotine and TSNAs can be separated into the TSNA fraction and the nicotine-enriched, TSNA-removed fraction by subjecting the membrane permeate fraction noted above to the reversed-phase partition chromatography according to the second embodiment.
- Agilent 1100 LC Chromatograph was used as the liquid chromatograph.
- Waters High Performance Carbohydrate Column 60A 4 ⁇ m (4.6 ⁇ 250 mm) was used as the column.
- the column temperature was set at 35°C.
- the sample injection amount was set at 8.0 ⁇ L.
- acetonitrile-refined water (3 : 1) was used as the moving phase.
- Extraction of shredded tobacco was conducted by mixing 200 g of shredded tobacco with 875 mL of water and stirring the mixture at 25°C. The extracted mixture thus obtained was filtered to obtain the extracted solution and the extraction residue. A regenerated tobacco web was obtained by subjecting the extraction residue to the paper-making process. Incidentally, the weight of the regenerated tobacco leaves was 100 g under the dried state, which was about half the weight of the original shredded tobacco.
- the extracted solution was mixed with 211 mL of water and subjected to membrane separating treatment by using a reverse osmosis membrane (Nanomax 95 available from Milipore Inc.) having a cut-off molecular weight of 100 to obtain a membrane non-permeate fraction (246 mL) and a membrane permeate fraction (840 mL).
- a reverse osmosis membrane Nax 95 available from Milipore Inc.
- the amounts of nitric acid and sugar (fructose and glucose) contained in the membrane non-permeate fraction and membrane permeate fraction thus obtained were analyzed to obtain the results given in Table 1 below. Table 1 also shows the analytical results of the extracted solution.
- the membrane non-permeate fraction was enriched in sugar and depleted in nitric acid.
- the membrane permeate fraction was depleted in sugar (0 in this case), and enriched in nitric acid.
- the entire amount (246 mL) of the membrane non-permeate fraction was added to 100 g of the regenerated tobacco web to obtain a regenerated tobacco material, and cigarettes were manufactured by using the resultant regenerated tobacco material.
- an additional extracting treatment was performed in exactly the same procedures as those of the extracting treatment described above, and a regenerated tobacco web was prepared from the extraction residue in the similar manner.
- the extracted solution was not subjected to the membrane separating treatment and was only concentrated by heating under vacuum. The entire amount of the concentrated extracted solution was added to the regenerated tobacco web to obtain a regenerated tobacco material, and cigarettes were manufactured by using the resultant regenerated tobacco material.
- Example 2 An extracting treatment similar to that in Example 1 was applied to shredded tobacco differing from that used in Example 1 to obtain an extracted solution and an extraction residue. A regenerated tobacco web was obtained by subjecting the extraction residue to the paper-making process.
- the extracted solution was subjected to a membrane separating treatment by using a reverse osmosis membrane (NTR-729HG available from Nitto Denko K.K.)
- NTR-729HG available from Nitto Denko K.K.
- the membrane non-permeate fraction thus obtained was added to the regenerated tobacco web to obtain a regenerated tobacco material, which was shredded so as to obtain shredded tobacco.
- an extracting treatment was carried out exactly as above, and a regenerated tobacco web was obtained by subjecting the resultant extraction residue to the paper-making process. Also, the extracted solution obtained by the extracting treatment was concentrated by heating under vacuum, and the entire amount of the concentrated extracted solution was added to the regenerated tobacco web to obtain a regenerated tobacco material, which was shredded to obtain shredded tobacco.
- the NO 3 amount in the shredded tobacco was lowered by about 95% in the shredded tobacco manufactured from the regenerated tobacco material obtained by adding the membrane non-permeate fraction to the regenerated tobacco web, compared with the shredded tobacco manufactured from the regenerated tobacco material to which was added the extracted solution not subjected to the membrane separating treatment in spite of the fact that the reduction in the nicotine amount was suppressed in the shredded tobacco involving the membrane non-permeate fraction.
- Cigarettes were manufactured by using each of the shredded tobacco described above so as to measure the NOx amount and the nicotine amount in the mainstream smoke as in Example 1. Table 4 shows the results. Table 4 Cigarette NOx amount in mainstream smoke Nicotine amount in mainstream smoke Per cigarette ( ⁇ g) Per mg of tar ( ⁇ g) Per cigarette (mg) Per mg of tar (mg) Shredded tobacco added with extracted solution 154 9.7 0.6 0.045 Shredded tobacco added with membrane non-permeate fraction 27 1.8 0.6 0.040
- the cigarette manufactured by using the shredded tobacco having the membrane non-permeate fraction added thereto was found to be fully comparable in the nicotine amount and to permit markedly decreasing the NOx amount, compared with the cigarette manufactured by using the shredded tobacco to which was added the extracted solution not subjected to the membrane separating treatment.
- Example 2 An extracting treatment similar to that in Example 1 was applied to shredded tobacco differing from that used in Example 1 to obtain an extracted solution and an extraction residue. A regenerated tobacco web was obtained by subjecting the extraction residue to the paper-making process.
- the extracted solution was subjected to the membrane separating treatment by using an ultrafiltration membrane (CF30-F-PT available from Nitto Denko K.K.; cut-off molecular weight of 50,000) and the membrane non-permeate fraction thus obtained was further subjected to the membrane separating treatment by using a reverse osmosis membrane (NTR-729HG available from Nitto Denko K.K).
- the membrane non-permeate fraction obtained was added to the regenerated tobacco web to obtain a regenerated tobacco material, which was shredded to obtain shredded tobacco.
- an extracting treatment was carried out exactly as above, and a regenerated tobacco web was obtained by subjecting the resultant extraction residue to the paper-making process. Also, the extracted solution obtained was concentrated by heating under vacuum, and the entire amount of the concentrated extracted solution was added to the regenerated tobacco web to obtain a regenerated tobacco material, which was shredded so as to obtain shredded tobacco.
- the shredded tobacco prepared from the regenerated tobacco material obtained by adding to the regenerated tobacco web the membrane non-permeate fraction obtained by subjecting the membrane permeate fraction in the ultrafiltration to the reverse osmosis filtration was found to decrease the NO 3 amount in the shredded tobacco by about 95% and also found to remove protein substantially completely in spite of the fact that the decrease of the nicotine amount was suppressed, compared with the shredded tobacco of the regenerated tobacco material involving the extracted solution that was not subjected to the membrane treatment.
- Cigarettes were manufactured by using each of the shredded tobacco described above so as to measure the NOx amount and the nicotine amount in the mainstream smoke as in Example 1. Table 6 shows the results. Table 6 Cigarette NOx amount in mainstream smoke Nicotine amount in mainstream smoke Per cigarette ( ⁇ g) Per mg of tar ( ⁇ g) Per cigarette (mg) Per mg of tar (mg) Shredded tobacco added with extracted solution 154 9.7 0.6 0.045 Shredded tobacco added with membrane non-permeate fraction 25 1.9 0.6 0.040
- the cigarette of the present invention manufactured by using the regenerated tobacco material obtained by adding to the regenerated tobacco web the membrane non-permeate fraction obtained by subjecting the membrane permeate fraction obtained in the ultrafiltration treatment to the reverse osmosis filtration was found to be fully comparable in the nicotine amount and to permit markedly decreasing the NOx amount, compared with the cigarette manufactured by using the shredded tobacco to which was added the extracted solution not subjected to the membrane separating treatment.
- Example 2 An extracting treatment similar to that in Example 1 was applied to shredded tobacco differing from that used in Example 1 to obtain an extracted solution and an extraction residue. A regenerated tobacco web was obtained by subjecting the extraction residue to the paper-making process.
- the extracted solution was subjected to the membrane separating treatment by using an ultrafiltration membrane (Biomax 10 available from Milipore Inc.; cut-off molecular weight of 50,000), and the membrane non-permeate fraction thus obtained was further subjected to the membrane separating treatment by using a reverse osmosis membrane (Nanomax 95 available from Milipore Inc.; cut-off molecular weight of about 100).
- the membrane non-permeate fraction obtained was added to the regenerated tobacco web to obtain a regenerated tobacco material, which was shredded to obtain shredded tobacco. Further, a cigarette was manufactured by using the shredded tobacco.
- an extracting treatment was carried out exactly as above, and a regenerated tobacco web was obtained by subjecting the resultant extraction residue to the paper-making process. Also, the extracted solution obtained by the extracting treatment was concentrated by the heating under vacuum, and the entire amount of the concentrated extracted solution was added to the regenerated tobacco web to obtain a regenerated tobacco material, which was shredded so as to obtain shredded tobacco. Further, a cigarette was manufactured by using the shredded tobacco.
- the cigarette of the present invention manufactured by using the regenerated tobacco material obtained by adding to the regenerated tobacco web the membrane non-permeate fraction obtained by subjecting the membrane permeate fraction in the ultrafiltration treatment to the reverse osmosis filtration was found to permit markedly decreasing the aromatic amines in the mainstream smoke, compared with the cigarette manufactured by using the shredded tobacco to which was added the extracted solution not subjected to the membrane separating treatment.
- shredded tobacco 100 g of shredded tobacco, which was a mixture of shredded tobacco (mixture of flue-cured species and burley species) and shredded central vain mixed at a weight ratio of 1 : 1 was mixed with 1,000 mL of water and stirred at 25°C to effect extraction of the shredded tobacco.
- the extracted mixture obtained was filtered to obtain an extracted solution and an extraction residue.
- the extraction residue was subjected to the paper-making process to obtain a regenerated tobacco web.
- the extracted solution was concentrated by the membrane separating treatment, and 1 mL of the concentrated solution was poured into a column (a diameter of 8 mm and a length of 300 mm) loaded with a polymethacrylic resin particles having a particle diameter of 200 to 600 ⁇ m (trade name: HP2MG available from Mitsubishi Chemical Co., Ltd.). Water was poured into the column as an eluent to obtain firstly 70 mL (fraction 1) and then 8030 mL (fraction 2).
- NN N'-nitrosonornicotine
- NK 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone
- NAT N'-nitrosoanatabine
- TSNAs were decreased from the initial amount by substantially 89% in fraction 1. NNK and NAT among TSNAs were completely removed in fraction 1. In addition, nicotine was decreased from the initial amount by only 3% in fraction 1.
- fraction 2 was discarded, and a regenerated tobacco material was prepared by adding fraction 1 to the regenerated tobacco web.
- a concentrated tobacco extracted solution and a regenerated tobacco web were prepared as in Example 5, except that the mixing ratio of the flue-cured species to the burley species was changed.
- 1 mL of the concentrated tobacco extracted solution was poured into a column (a diameter of 10 mm and a length of 250 mm) loaded with a phenyl group-modified polyvinyl resin having a particle diameter of 50 to 150 ⁇ m (trade name of TOYOPEARL Phenyl 650C available from Toso Inc.). Water used as an eluent was poured into the column to obtain first 28 mL (raction 1), and then 115 mL (fraction 2).
- TSNAs were decreased from the initial amount by substantially 91% in fraction 1. Also, NNK, NAT and NAB among TSNAs were removed completely in fraction 1. In addition, nicotine was not decreased at all in fraction 1.
- fraction 2 was discarded, and a regenerated tobacco material was prepared by adding fraction 1 to the regenerated tobacco web.
- a concentrated tobacco extracted solution and a regenerated tobacco web were prepared as in Example 1, except that the mixing ratio of the flue-cured species to the burley species was changed. 0.02 mL of the concentrated tobacco extracted solution was poured into a column (a diameter of 6 mm and a length of 150 mm) loaded with a butyl group-modified silica based resin having an average particle diameter of 15 ⁇ m (trade name of Pack C4 available from YMC Inc. Water used as an eluent was poured into the column to obtain first 600 mL (fraction 1), and then 400 mL (fraction 2). The amounts of nicotine, NNN, NNK, NAT, and NAB were analyzed for the extracted solution before the fractionation (untreated extracted solution) and each fraction. Table 10 shows the results. The nicotine reduction rate and the TSNA reduction rate are also shown in Table 10.
- TSNAs were decreased by 100% in fraction 2.
- the nicotine reduction amount from the initial amount was found to be only 33% in fraction 2.
- fraction 1 was discarded, and a regenerated tobacco material was prepared by adding fraction 2 to the regenerated tobacco web.
- the TSNA reduction rate was not lower than 90%, and a fraction can be obtained in which the nicotine reduction rate is lower than 35%, in the case of using a stationary phase material having hydrophobic groups formed of hydrocarbon groups having at most 6 carbon atoms.
- a concentrated tobacco extracted solution and a regenerated tobacco web were prepared as in Example 5, except that the mixing ratio of the flue-cured species to the burley species was changed.
- 0.02 mL of the concentrated tobacco extracted solution was poured into a column (a diameter of 4.6 mm and a length of 150 mm) loaded with an octyl group-modified silica-based resin having an average particle diameter of 5 ⁇ m (trade name of XDB-C8 available from Alingent Inc).
- Water used as an eluent was poured into the column to obtain first 200 mL (fraction 1), then 200 mL (fraction 2), and finally 400 mL (fraction 3).
- the amounts of nicotine, NNN, NNK, NAT, and NAB were analyzed for the extracted solution before the fractionation (untreated extracted solution) and each fraction.
- Table 11 shows the results.
- the nicotine reduction rate and the TSNA reduction rate are also shown in Table 11.
- TSNAs were removed completely in fraction 3.
- nicotine reduction rate was 56% in fraction 3.
- fractions 1 and 2 were discarded, and a regenerated tobacco material was prepared by adding fraction 3 to the regenerated tobacco web.
- a concentrated tobacco extracted solution and a regenerated tobacco web were prepared as in Example 1, except that the mixing ratio of the flue-cured species to the burley species was changed.
- 0.02 mL of the concentrated tobacco extracted solution was poured into a column (a diameter of 6 mm and a length of 150 mm) loaded with a octadecyl group-modified silica-based resin having an average particle diameter of 15 ⁇ m (trade name of ODS-AP available from YMC Inc).
- Water used as an eluent was poured into the column to obtain first 400 mL (fraction 1), then 200 mL (fraction 2), and finally 200 mL (fraction 3).
- the amounts of nicotine, NNN, NNK, NAT, and NAB were analyzed for the extracted solution before the fractionation (untreated extracted solution) and each fraction.
- Table 12 shows the results.
- the nicotine reduction rate and the TSNA reduction rate are also shown in Table 12.
- TSNAs were removed completely in fraction 3.
- the nicotine reduction rate for fraction 3 was found to be 65%.
- fractions 1 and 2 were discarded, and a regenerated tobacco material was prepared by adding fraction 3 to the regenerated tobacco web.
- TSNAs were significantly removed in each of fractions 1 and 2. However, nicotine was removed completely in these fractions. Clearly, it is impossible to obtain a regenerated tobacco material containing nicotine in the case of using any of fractions 1 and 2.
- TSNAs were significantly removed in fraction 1. However, nicotine was also removed completely. On the other hand, the initial nicotine amount was maintained by 100% in fraction 2. However, the TSNA reduction rate was only 26%. Clearly, it is impossible to obtain a regenerated tobacco material containing a significant amount of nicotine and substantially free from TSNA in the case of using any of fractions 1 and 2.
- TSNAs were significantly removed in fractions 1 to 5.
- the nicotine reduction rate was not lower than about 70%. It follows that it is impossible to obtain a regenerated tobacco material containing a significant amount of nicotine and substantially free from TSNA by using any of fractions 1 to 5.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003128104 | 2003-05-06 | ||
| JP2003384083 | 2003-11-13 | ||
| PCT/JP2004/006001 WO2004098323A1 (fr) | 2003-05-06 | 2004-04-26 | Procédé de production de tabac régénéré |
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| EP1623634A1 true EP1623634A1 (fr) | 2006-02-08 |
| EP1623634A4 EP1623634A4 (fr) | 2011-02-23 |
| EP1623634B1 EP1623634B1 (fr) | 2013-06-12 |
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| EP04729526.6A Expired - Lifetime EP1623634B1 (fr) | 2003-05-06 | 2004-04-26 | Procédé de production de tabac régénéré |
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| US (1) | US7677253B2 (fr) |
| EP (1) | EP1623634B1 (fr) |
| JP (1) | JP3867098B2 (fr) |
| KR (1) | KR100730631B1 (fr) |
| CA (1) | CA2524714C (fr) |
| DK (1) | DK1623634T3 (fr) |
| ES (1) | ES2414867T3 (fr) |
| PT (1) | PT1623634E (fr) |
| RU (1) | RU2310353C2 (fr) |
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| WO (1) | WO2004098323A1 (fr) |
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| JP6693747B2 (ja) * | 2012-12-21 | 2020-05-13 | フィリップ・モーリス・プロダクツ・ソシエテ・アノニム | 植物体中のたばこ特異的ニトロソアミンの低減 |
| PL3200624T3 (pl) | 2014-09-30 | 2024-04-02 | Philip Morris Products S.A. | Odzyskiwanie składników tytoniowych z procesu przetwarzania |
| EP3269260A4 (fr) * | 2015-03-10 | 2018-10-10 | Japan Tobacco, Inc. | Procédé de fabrication d'une matière régénérée pour tabac à mâcher, et produit de tabac à mâcher |
| GB201521626D0 (en) * | 2015-12-08 | 2016-01-20 | British American Tobacco Co | Tobacco composition |
| WO2019097641A1 (fr) * | 2017-11-16 | 2019-05-23 | 日本たばこ産業株式会社 | Procédé de fabrication d'une charge de tabac contenant un parfum, charge de tabac contenant un parfum et inhalateur d'arôme de type chauffant |
| WO2019229850A1 (fr) | 2018-05-29 | 2019-12-05 | 日本たばこ産業株式会社 | Papier à rouler pour article à fumer du type à chauffage sans combustion, article à fumer de type à chauffage sans combustion et système à fumer de type à chauffage électrique |
| US12063953B2 (en) | 2019-09-11 | 2024-08-20 | Nicoventures Trading Limited | Method for whitening tobacco |
| CA3150662A1 (fr) | 2019-09-11 | 2021-03-18 | Michael Andrew Zawadzki | Procedes alternatifs de blanchiment du tabac |
| US11369131B2 (en) | 2019-09-13 | 2022-06-28 | Nicoventures Trading Limited | Method for whitening tobacco |
| CN111035053B (zh) * | 2019-11-27 | 2022-07-05 | 内蒙古昆明卷烟有限责任公司 | 烟蒂焦油中致香成分的提取方法及其在卷烟中的应用 |
| US11937626B2 (en) | 2020-09-04 | 2024-03-26 | Nicoventures Trading Limited | Method for whitening tobacco |
| KR20240124344A (ko) | 2021-12-14 | 2024-08-16 | 니뽄 다바코 산교 가부시키가이샤 | 식물 엑기스의 제조 방법 |
| CN117186990A (zh) * | 2022-05-31 | 2023-12-08 | 中国烟草总公司郑州烟草研究院 | 一种菊苣特色风味香料的制备方法、菊苣特色风味香料以及卷烟 |
| JPWO2024127603A1 (fr) | 2022-12-15 | 2024-06-20 | ||
| CN116042315B (zh) * | 2022-12-23 | 2024-11-01 | 中国烟草总公司郑州烟草研究院 | 一种黄姜花香料及其制备方法与其在烟草制品中的应用 |
| WO2024252653A1 (fr) * | 2023-06-09 | 2024-12-12 | 日本たばこ産業株式会社 | Matériau de tabac, procédé de production et article à fumer |
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- 2004-04-26 RU RU2005137852/12A patent/RU2310353C2/ru active
- 2004-04-26 JP JP2005505981A patent/JP3867098B2/ja not_active Expired - Lifetime
- 2004-04-26 ES ES04729526T patent/ES2414867T3/es not_active Expired - Lifetime
- 2004-04-26 KR KR1020057020809A patent/KR100730631B1/ko not_active Expired - Fee Related
- 2004-04-26 WO PCT/JP2004/006001 patent/WO2004098323A1/fr not_active Ceased
- 2004-04-26 EP EP04729526.6A patent/EP1623634B1/fr not_active Expired - Lifetime
- 2004-04-26 DK DK04729526.6T patent/DK1623634T3/da active
- 2004-04-26 CA CA002524714A patent/CA2524714C/fr not_active Expired - Fee Related
- 2004-04-26 PT PT47295266T patent/PT1623634E/pt unknown
- 2004-04-30 TW TW093112156A patent/TWI351257B/zh not_active IP Right Cessation
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2005
- 2005-11-03 US US11/265,305 patent/US7677253B2/en active Active
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007053097A1 (fr) | 2005-11-07 | 2007-05-10 | Njette Ab | Nicotine a teneur reduite en nitrosamines |
| US10159273B2 (en) | 2011-01-28 | 2018-12-25 | R.J. Reynolds Tobacco Company | Tobacco-derived casing composition |
| EP2667735B1 (fr) | 2011-01-28 | 2017-07-05 | R. J. Reynolds Tobacco Company | Composition d'enveloppe à base de tabac |
| EP2687110A4 (fr) * | 2011-03-15 | 2014-11-12 | Japan Tobacco Inc | Procédé et dispositif de production de matériau de tabac régénéré |
| US9301544B2 (en) | 2013-03-14 | 2016-04-05 | R.J. Reynolds Tobacco Company | Protein-enriched tobacco-derived composition |
| WO2014159617A1 (fr) * | 2013-03-14 | 2014-10-02 | R. J. Reynolds Tobacco Company | Composition dérivée du tabac enrichie en protéines |
| US11166485B2 (en) | 2013-03-14 | 2021-11-09 | R.J. Reynolds Tobacco Company | Protein-enriched tobacco-derived composition |
| US11375741B2 (en) | 2013-03-14 | 2022-07-05 | R.J. Reynolds Tobacco Company | Protein-enriched tobacco-derived composition |
| WO2014140346A1 (fr) * | 2013-03-15 | 2014-09-18 | Philip Morris Products S.A | Procédés de réduction d'une ou plusieurs nitrosamines spécifiques du tabac dans une matière de tabac |
| US11612183B2 (en) | 2015-12-10 | 2023-03-28 | R.J. Reynolds Tobacco Company | Protein-enriched tobacco composition |
| US12178237B2 (en) | 2015-12-10 | 2024-12-31 | R.J. Reynolds Tobacco Company | Protein-enriched tobacco composition |
| CN106509979A (zh) * | 2016-12-26 | 2017-03-22 | 福建中烟工业有限责任公司 | 一种组合物及使用该组合物制备烟草提取物的方法 |
| CN111713730A (zh) * | 2020-07-17 | 2020-09-29 | 杨伟祖 | 一种烟用增香减害颗粒及其制备方法和应用 |
| CN111713730B (zh) * | 2020-07-17 | 2021-04-30 | 杨伟祖 | 一种烟用增香减害颗粒及其制备方法和应用 |
| EP4449892A4 (fr) * | 2021-12-14 | 2025-12-17 | Japan Tobacco Inc | Tabac, son procédé de production et produit de tabac |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2524714A1 (fr) | 2004-11-18 |
| TWI351257B (en) | 2011-11-01 |
| JPWO2004098323A1 (ja) | 2006-07-13 |
| WO2004098323A1 (fr) | 2004-11-18 |
| CA2524714C (fr) | 2009-06-02 |
| JP3867098B2 (ja) | 2007-01-10 |
| RU2005137852A (ru) | 2006-04-27 |
| RU2310353C2 (ru) | 2007-11-20 |
| EP1623634A4 (fr) | 2011-02-23 |
| TW200425844A (en) | 2004-12-01 |
| HK1091380A1 (zh) | 2007-01-19 |
| ES2414867T3 (es) | 2013-07-23 |
| US20060065279A1 (en) | 2006-03-30 |
| KR100730631B1 (ko) | 2007-06-20 |
| DK1623634T3 (da) | 2013-07-15 |
| KR20060004975A (ko) | 2006-01-16 |
| US7677253B2 (en) | 2010-03-16 |
| EP1623634B1 (fr) | 2013-06-12 |
| PT1623634E (pt) | 2013-08-23 |
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